催化学报

催化学报 ›› 2011, Vol. 32 ›› Issue (9): 1446-1451.DOI: 10.1016/S1872-2067(10)60254-9

• 研究快讯 • 上一篇    下一篇

2,2,6,6-四甲基哌啶-1-氧自由基促进的钒基催化剂催化苯直接氧化制苯酚

陈佳琦1,2, 高爽1,*, 李军1, 吕迎1   

  1. 1中国科学院大连化学物理研究所, 辽宁大连 116023; 2中国科学院研究生院, 北京 100049
  • 收稿日期:2011-05-28 修回日期:2011-07-07 出版日期:2011-09-09 发布日期:2015-01-24

2,2,6,6-Tetramethylpiperidine-1-Oxyl-Promoted Hydroxylation of Benzene to Phenol over a Vanadium-Based Catalyst Using Molecular Oxygen

CHEN Jiaqi1,2, GAO Shuang1,*, LI Jun1, LÜ Ying1   

  1. 1Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China; 2Graduate School of the Chinese Academy of Sciences, Beijing 100049, China
  • Received:2011-05-28 Revised:2011-07-07 Online:2011-09-09 Published:2015-01-24

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1020

被引次数

31

摘要： 以钒基化合物为催化剂, 在 TEMPO (2,2,6,6-四甲基哌啶-1-氧自由基) 存在下, 能形成快速催化分子氧氧化苯制苯酚的催化体系. 在反应过程中, 由类似芬顿试剂反应过程生成的羟基自由基亲核进攻苯环, 形成羟基环己二烯自由基; 该羟基氢可在 TEMPO 存在的催化体系中消除, 同时苯环氢可立即转移至氧原子而生成苯酚. 在以 [(CH3)4N]4-PMo11VO40 为催化剂的体系中, 反应 1 h 苯酚收率可从不加 TEMPO 时的 1.2% 提高到 8.4%; 而以 V-AlPO5 为催化剂时, 苯酚收率可从不加 TEMPO 时的 5.0% 提高到 9.5%, 且选择性均较高.

关键词: 2,2,6,6-四甲基哌啶-1-氧自由基, 钒, 苯, 羟基化, 分子氧, 苯酚

Abstract: Rapid benzene hydroxylation was achieved using a reaction system that consisted of a vanadium-based catalyst, ascorbic acid, and 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) with molecular oxygen as the oxidant. The hydroxyl radicals that form by a Fenton-type process attack the benzene ring to produce a hydroxycyclohexadienyl radical. The hydroxyl hydrogen is then abstracted quickly in the presence of TEMPO and phenol forms by the transfer of a hydrogen atom from the benzene ring to oxygen. Over the [(CH3)4N]4-PMo11VO40 catalyst the phenol yield reached 8.3% with a selectivity of 95% in 1 h while trace amounts of phenol were obtained in the normal system without TEMPO.

Key words: 2,2,6,6-tetramethylpiperidine-1-oxyl, vanadium, benzene, hydroxylation, phenol, molecular oxygen